CN114478209A - Method for preparing methoxy acetone through continuous catalytic dehydrogenation of propylene glycol methyl ether - Google Patents

Method for preparing methoxy acetone through continuous catalytic dehydrogenation of propylene glycol methyl ether Download PDF

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CN114478209A
CN114478209A CN202210066097.0A CN202210066097A CN114478209A CN 114478209 A CN114478209 A CN 114478209A CN 202210066097 A CN202210066097 A CN 202210066097A CN 114478209 A CN114478209 A CN 114478209A
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catalyst
temperature
propylene glycol
reaction
methyl ether
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CN114478209B (en
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郑金欣
晁哲
万克柔
程杰
高明明
林涛
张力
张炳亮
李国斌
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Kaili Catalyst New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses a method for preparing methoxy acetone by continuous catalytic dehydrogenation of propylene glycol monomethyl ether, which comprises the steps of carrying out catalytic dehydrogenation in a fixed bed, preparing a catalyst by fractional precipitation, preparing an oxide carrier by primary precipitation to provide a loading place for active components, and distributing the carrier serving as a dispersing agent of the active components among the active components to prevent a large amount of active metals from agglomerating at high temperature; the secondary precipitation loads active components such as copper, nickel, cobalt and the like, and a metal complexing agent is added, so that the agglomeration of the active metals can be further reduced, and the performance of the catalyst is improved. The catalyst of the invention has a raw material conversion rate of more than 60% and a selectivity of more than 95% at a reaction temperature of 220-280 ℃. The catalyst provided by the invention has good catalytic performance, the activation temperature required by the catalyst is low, more dehydration byproducts are prevented from being generated under the high-temperature condition, and the later separation cost can be reduced. Meanwhile, the catalyst is low in cost, green and environment-friendly, and can be applied to continuous industrial production.

Description

Method for preparing methoxy acetone through continuous catalytic dehydrogenation of propylene glycol methyl ether
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method and application of a catalyst for synthesizing methoxy acetone.
Background
The methoxy acetone has wide application, can be used as a low-toxicity pesticide intermediate, and is a main synthetic raw material of the herbicide metolachlor; it can also be used as high-efficiency organic solvent for producing fine chemicals such as cleaning agent and paint. At present, methoxy acetone is mainly obtained by catalytic dehydrogenation or oxidation of propylene glycol methyl ether. Since the methoxy induction effect of the raw material causes difficulty in preparing the target product methoxy acetone, a proper catalyst is needed to improve the reaction conversion rate. The raw material is easy to generate dehydration byproducts under the high-temperature condition, and the boiling points of the raw material and the product are close and difficult to separate, so that the subsequent treatment cost is increased, and therefore, the high-efficiency catalyst with low cost can greatly reduce the production cost of enterprises.
Chinese patent CN 1474798A discloses a method for preparing methoxy acetone by catalytic dehydrogenation with copper chromite as a catalyst, which contains heavy metal chromium and has hidden danger of environmental pollution. Chinese patent CN 1403431A discloses a catalyst which takes Cu, Ag or Mo as a main body of the catalyst, Mg, Cr, K and other metals as auxiliary agents and silica gel, alumina and the like as carriers, the preparation method is an impregnation method, and the evaluation reaction temperature of the catalyst is 250-350 ℃. In the catalyst prepared by the impregnation method, the metal is mainly attached to the surface of the carrier, loss and inactivation are easy, in addition, the reaction temperature is higher, more byproducts are likely to be generated, and the metal on the surface is also easy to sinter. Chinese patent CN 101314562a discloses a method for preparing methoxy acetone by catalytic oxidation with 2,2,6, 6-tetramethylpiperidine-1-oxygen radical and nitrite or nitrate as catalysts, oxygen or hypohalite as oxidants, and solvent method, the method has poor automation degree, and the subsequent catalyst and product separation is complex. Chinese patent CN 105384616a discloses a method for preparing methoxy acetone by catalytic dehydrogenation of a catalyst with Ni and Cr as active components and gamma-alumina as a carrier, which comprises the following raw materials: the water is 4:1 (mol ratio). The catalyst in the method relates to heavy metal chromium, which may cause pollution to the environment, and in addition, the water content of the raw material is too high, which reduces the production efficiency.
In the prior art, the methoxy acetone is mostly prepared by adopting a copper-based composite catalyst in a catalytic manner, and the contradiction that the conversion rate and the selectivity cannot be considered exists mainly, so that the preparation process method of the catalyst for synthesizing the methoxy acetone still needs to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the method for preparing the methoxy acetone by continuously catalyzing and dehydrogenating the propylene glycol monomethyl ether.
In order to achieve the purpose, the invention adopts the technical scheme that: propylene glycol methyl ether continuous catalytic dehydrogenation is carried out in a fixed bed to prepare methoxy acetone, a catalyst for catalytic dehydrogenation is prepared by fractional precipitation, a carrier is prepared by the first-level precipitation, active components are loaded by the second-level precipitation, the carrier is any one or two of zinc oxide, aluminum oxide and magnesium oxide, and the active components are any one or two of copper, nickel and cobalt or oxides thereof; the specific preparation method of the catalyst comprises the following steps:
(1) primary precipitation: under the conditions of heating and stirring, dropwise adding a precipitator into a soluble metal salt aqueous solution of the carrier, stopping dropwise adding the precipitator when the pH value of a mixed solution is 7-8, continuously stirring at a constant temperature for 30-120 min for carrying out a precipitation reaction, and then carrying out aging, suction filtration, washing, drying, roasting and grinding to obtain the carrier;
(2) secondary precipitation: uniformly mixing a carrier and a soluble metal salt aqueous solution of an active component, adding a metal complexing agent, dropwise adding a precipitator under the conditions of heating and stirring, stopping dropwise adding the precipitator when the pH value of the mixed solution is 7-8, continuously stirring at a constant temperature for 30-120 min for precipitation reaction, and then aging, filtering, washing, drying, roasting and grinding to obtain a catalyst precursor; wherein, the carrier accounts for 20-70% of the mass of the catalyst precursor, and the active component accounts for 30-80% of the mass of the catalyst precursor;
(3) uniformly mixing a catalyst precursor and graphite powder, and then tabletting and forming to obtain a catalyst; wherein, the adding amount of the graphite powder is 0.5 to 5 percent of the mass of the catalyst precursor.
In the catalyst, the carrier is preferably a mixture of zinc oxide or magnesium oxide and aluminum oxide, wherein the molar ratio of the zinc oxide or magnesium oxide to the aluminum oxide is 0.3-3: 1; the active component is preferably any one of copper, cobalt or their oxides.
In the preparation method of the catalyst, the carrier preferably accounts for 30-60% of the mass of the catalyst precursor, and the active component preferably accounts for 40-70% of the mass of the catalyst precursor; the adding amount of the graphite powder is 2-5% of the mass of the catalyst precursor.
In the preparation method of the catalyst, the soluble metal salt of the carrier and the soluble metal salt of the active component are nitrates; the precipitator is any one of sodium carbonate, sodium bicarbonate and potassium carbonate; the metal complexing agent is any one of sodium ethylene diamine tetracetate, sodium aminotriacetate and ethanolamine, and the addition amount of the complexing agent is 0.1-5% of the mass of the catalyst precursor.
In the preparation method of the catalyst, the heating temperature is 50-95 ℃, and the stirring speed is 50-300 r/min; the aging temperature is 50-95 ℃ and the aging time is 1-24 h; the roasting temperature is 300-700 ℃, and the roasting time is 2-10 h. Preferably, the heating temperature is 60-90 ℃, and the stirring speed is 100-200 r/min; the aging temperature is 60-90 ℃, and the aging time is 5-20 h; the roasting temperature is 350-600 ℃, and the roasting time is 3-8 h.
When the propylene glycol methyl ether is subjected to continuous catalytic dehydrogenation in the fixed bed to prepare the methoxy acetone, the catalyst is preferably reduced by hydrogen before reaction, the reduction temperature is 210-300 ℃, and the reduction time is 2-20 hours.
When the propylene glycol methyl ether continuous catalytic dehydrogenation is carried out in the fixed bed to prepare the methoxy acetone, the reaction temperature of the catalytic dehydrogenation is 200-300 ℃, the reaction pressure is 0-0.5 MPa, and the reaction space velocity is 0.3-3 h-1And filling nitrogen in the reaction process, wherein the flow rate of the nitrogen is 50-1000 mL/min.
The invention has the beneficial effects that:
(1) the non-noble metal and the non-heavy metal are used as the active components of the catalyst, and the prepared catalyst is low in cost and environment-friendly.
(2) The invention adopts primary precipitation to prepare the alumina, zinc oxide or magnesium oxide carrier, and provides a loading place for active components. Meanwhile, the carrier can be used as a dispersing agent of the active components and distributed among the active components, so that the active component metals can be prevented from being greatly agglomerated under the high-temperature condition to a certain extent, and the performances of the catalyst, such as activity, selectivity, service life and the like, can be improved. When the method adopts the secondary precipitation of the active components, the metal complexing agent is added, so that the agglomeration of the active metals can be further reduced, and the improvement of the performance of the catalyst is facilitated.
(3) The catalyst has good catalytic performance, the activation temperature required by the catalyst is low, more dehydration byproducts can be prevented from being generated under the high-temperature condition, and the later separation cost can be reduced. Meanwhile, the catalyst is used for preparing methoxy acetone by catalytic dehydrogenation of propylene glycol monomethyl ether, and the conversion rate of raw materials can reach more than 60% and the selectivity can reach more than 95% at the reaction temperature of 220-280 ℃. And can realize continuous production, and is beneficial to the later-stage industrial production.
Detailed Description
The technical solution of the present invention is further illustrated in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Primary precipitation: 147.11g of Al (NO)3)3·9H2O and 73.45g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for precipitation reaction, and then putting into an oven at 80 ℃ for aging for 12 h. After aging, carrying out suction filtration, washing and drying, roasting at 450 ℃ for 4h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 1.26: 1.
(2) 40g of a zinc oxide-alumina composite carrier and 183.49g of Cu (NO)3)2·3H2Adding O and 1g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into an oven at 80 ℃ for aging for 12 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting for 4h at 450 ℃ to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 40% of the mass of the catalyst precursor, and the copper oxide accounts for 60% of the mass of the catalyst precursor.
(3) And uniformly mixing 100g of catalyst precursor and 3g of graphite powder, and tabletting to obtain the catalyst.
(4) 50g of catalyst is filled in the middle of a fixed bed reaction tube, quartz sand is filled in the upper part and the lower part of the catalyst, reduction is carried out after filling, the reduction atmosphere is hydrogen, the reduction temperature is 240 ℃, and the reduction time is 4 hours. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 220 ℃, the reaction pressure is 0MPa, and the reaction airspeed is 2h-1Nitrogen is filled in the reaction process, the flow rate of the nitrogen is 300mL/min, and the reaction result is shown in Table 1.
Example 2
In step (2) of this example, 40g of a zinc oxide-alumina composite carrier and 233.04g of Co (NO)3)2·6H2Adding O and 1g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into an oven at 80 ℃ for aging for 12 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting for 4h at 450 ℃ to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 40% of the mass of the catalyst precursor, and the cobalt oxide accounts for 60% of the mass of the catalyst precursor.
The steps (1), (3) and (4) of this example are the same as those of example 1. The reaction results are shown in Table 1.
Example 3
In step (1) of this example, 147.11g of Al (NO)3)3·9H2O and 127.24g Mg (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for precipitation reaction, and then putting into an oven at 80 ℃ for aging for 12 h. After aging, carrying out suction filtration, washing and drying, roasting at 450 ℃ for 4h, and grinding to particle size<500 meshes to obtain the magnesia-alumina composite carrier, wherein the molar ratio of magnesia to alumina is 2.53: 1.
in step (2) of this example, 40g of a magnesia-alumina composite carrier and 183.49g of Cu (NO)3)2·3H2Adding O and 1g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix,the stirring speed is set to be 200r/min, the circulation heating is started, and the heating temperature is set to be 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into an oven at 80 ℃ for aging for 12 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting for 4h at 450 ℃ to obtain a catalyst precursor, wherein the magnesium oxide-aluminum oxide composite carrier accounts for 40% of the mass of the catalyst precursor, and the copper oxide accounts for 60% of the mass of the catalyst precursor.
Steps (3) and (4) in this example are the same as in example 1. The reaction results are shown in Table 1.
Example 4
In step (1) of this example, 330.99g of Al (NO)3)3·9H2O and 55.09g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a sodium carbonate aqueous solution with the mass concentration of 20% into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for carrying out precipitation reaction, and then putting into an oven at 80 ℃ for aging for 12 h. After aging, carrying out suction filtration, washing and drying, roasting at 450 ℃ for 4h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 0.42: 1.
in step (2) of this example, 60g of a zinc oxide-alumina composite carrier and 122.33g of Cu (NO)3)2·3H2Adding O and 1g of sodium nitrilotriacetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, starting circulating heating, and setting the heating temperature at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into an oven at 80 ℃ for aging for 12 h. After aging, carrying out suction filtration, washing,Drying and roasting at 450 ℃ for 4h to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 60% of the mass of the catalyst precursor, and the copper oxide accounts for 40% of the mass of the catalyst precursor.
Step (3) and step (4) of this example are the same as in example 1. The reaction results are shown in Table 1.
Example 5
In step (1) of this example, 73.55g of Al (NO)3)3·9H2O and 73.45g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 85 ℃. And (3) when the temperature is stabilized at 85 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for carrying out precipitation reaction, and then putting into an oven at 85 ℃ for aging for 8 h. After aging, carrying out suction filtration, washing and drying, roasting at 400 ℃ for 5h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 2.52: 1.
in step (2) of this example, 30g of a zinc oxide-alumina composite carrier and 214.08g of Cu (NO)3)2·3H2Adding O and 2.5g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, and starting circulating heating at 85 ℃. And (3) when the temperature is stabilized at 85 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into an oven at 80 ℃ for aging for 12 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting at 400 ℃ for 5 hours to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 30% of the mass of the catalyst precursor, and the copper oxide accounts for 70% of the mass of the catalyst precursor.
Step (3) of this example is the same as example 1.
Procedure of the present example(4) And filling 50g of catalyst into the middle part of a fixed bed reaction tube, filling quartz sand into the upper part and the lower part of the catalyst, and reducing after filling, wherein the reducing atmosphere is hydrogen, the reducing temperature is 280 ℃, and the reducing time is 3 hours. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 220 ℃, the reaction pressure is 0MPa, and the reaction airspeed is 2h-1Nitrogen is filled in the reaction process, the flow rate of the nitrogen is 300mL/min, and the reaction result is shown in Table 1.
Example 6
In step (1) of this example, 220.66g of Al (NO)3)3·9H2O and 110.18g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 90 ℃. And (3) when the temperature is stabilized at 90 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for precipitation reaction, and then putting the mixed solution into a 90 ℃ oven for aging for 10 h. After aging, carrying out suction filtration, washing and drying, roasting at 550 ℃ for 4h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 1.26: 1.
in step (2) of this example, 60g of a zinc oxide-alumina composite carrier and 122.33g of Cu (NO)3)2·3H2Adding O and 0.8g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, and starting circulating heating at 90 ℃. And (3) when the temperature is stabilized at 90 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into a 90 ℃ oven for aging for 10 h. After the aging is finished, carrying out suction filtration, washing and drying, and roasting at 550 ℃ for 4h to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 60% of the mass of the catalyst precursor, and the copper oxide accounts for40% of the mass of the catalyst precursor.
In step (3) of this example, 100g of the catalyst precursor in step (2) and 4g of graphite powder are uniformly mixed and then tableted to obtain the catalyst.
In the step (4) of this example, 50g of the catalyst was filled into the middle of the fixed bed reaction tube, and the catalyst was filled with quartz sand from top to bottom, and after filling, reduction was carried out in a reducing atmosphere of hydrogen at a reducing temperature of 260 ℃ for a reducing time of 3 hours. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 220 ℃, the reaction pressure is 0MPa, and the reaction airspeed is 2h-1Nitrogen is filled in the reaction process, the flow rate of the nitrogen is 300mL/min, and the reaction result is shown in Table 1.
Example 7
In step (1) of this example, 147.11g of Al (NO)3)3·9H2O and 73.45g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at 60 ℃. And (3) when the temperature is stabilized at 60 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring at a constant temperature for 2h for carrying out a precipitation reaction, and then putting into a 60 ℃ oven for aging for 20 h. After aging, carrying out suction filtration, washing and drying, roasting at 400 ℃ for 5h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 1.26: 1.
in step (2) of this example, 40g of a zinc oxide-alumina composite carrier and 183.49g of Cu (NO)3)2·3H2Adding O and 1g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, and starting circulating heating at 60 ℃. When the temperature is stabilized at 60 +/-2 ℃, dropwise adding a potassium carbonate aqueous solution with the mass concentration of 20% into a glass stirring kettle until the pH value of the mixed solution is equal toStopping dropwise adding when the temperature is 7-8 ℃, continuously stirring for 2h at constant temperature, and then putting into an oven with the temperature of 60 ℃ for aging for 20 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting at 400 ℃ for 5 hours to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 40% of the mass of the catalyst precursor, and the copper oxide accounts for 60% of the mass of the catalyst precursor.
Step (3) of this example is the same as example 1.
In the step (4) of this example, 50g of the catalyst was filled into the middle of the fixed bed reaction tube, and the catalyst was filled with quartz sand from top to bottom, and after filling, reduction was performed under hydrogen at 230 ℃ for 10 hours. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 220 ℃, the reaction pressure is 0MPa, and the reaction airspeed is 2h-1Nitrogen is filled in the reaction process, the flow rate of the nitrogen is 300mL/min, and the reaction result is shown in Table 1.
Example 8
The steps (1), (2) and (3) of this example are the same as those of example 1.
In the step (4) of this example, 50g of the catalyst was filled into the middle of the fixed bed reaction tube, and the catalyst was filled with quartz sand from top to bottom, and after filling, reduction was performed in a reducing atmosphere of hydrogen at a reducing temperature of 250 ℃ for 4 hours. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 230 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1h-1And nitrogen is filled in the reaction process, and the nitrogen flow is 200 mL/min. The reaction results are shown in Table 1.
Example 9
The steps (1), (2) and (3) of this example are the same as those of example 1.
In the step (4) of this example, 50g of the catalyst was filled into the middle of the fixed bed reaction tube, and the catalyst was filled with quartz sand from top to bottom, and after filling, reduction was performed in a reducing atmosphere of hydrogen at a reducing temperature of 250 ℃ for 4 hours. Starting a feeding reaction after the reduction is finished, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, and a heating wire is adopted at a feeding endPreheating, wherein the reaction temperature is 280 ℃, the reaction pressure is 0.5MPa, and the reaction space velocity is 2.5h-1And nitrogen is filled in the reaction process, and the nitrogen flow is 500 mL/min. The reaction results are shown in Table 1.
Example 10
In step (1) of this example, 147.11g of Al (NO)3)3·9H2O and 73.45g Zn (NO)3)2·6H2Placing O in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the nitrate, setting the stirring speed at 200r/min, and starting circulating heating at a heating temperature of 70 ℃. And (3) when the temperature is stabilized at 70 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH value of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for precipitation reaction, and then putting into a 70 ℃ oven for aging for 10 h. After aging, carrying out suction filtration, washing and drying, roasting at 500 ℃ for 6h, and grinding to particle size<500 meshes to obtain the zinc oxide-alumina composite carrier, wherein the molar ratio of zinc oxide to alumina is 1.26: 1.
in step (2) of this example, 40g of a zinc oxide-alumina composite carrier and 183.49g of Cu (NO)3)2·3H2Adding O and 1g of sodium ethylene diamine tetracetate into a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to fully mix the materials, setting the stirring speed at 200r/min, starting circulating heating, and setting the heating temperature at 70 ℃. And (3) when the temperature is stabilized at 70 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring for 2h at constant temperature, and then putting the mixed solution into a 70 ℃ oven for aging for 10 h. And after the aging is finished, carrying out suction filtration, washing and drying, and roasting for 6h at 500 ℃ to obtain a catalyst precursor, wherein the zinc oxide-aluminum oxide composite carrier accounts for 40% of the mass of the catalyst precursor, and the copper oxide accounts for 60% of the mass of the catalyst precursor.
Step (3) of this example is the same as example 1.
In the step (4) of this example, 50g of the catalyst was filled in the middle of the fixed bed reaction tube, and the catalyst was filled with quartz sand from the top and bottom, and after filling, reduction was carried out, and further reduction was carried outThe original atmosphere is hydrogen, the reduction temperature is 250 ℃, and the reduction time is 4 h. After the reduction is finished, starting a feeding reaction, wherein the raw material is propylene glycol methyl ether with the water content of 5 wt.%, the feeding end is preheated by a heating wire, the reaction temperature is 240 ℃, the reaction pressure is 0MPa, and the reaction airspeed is 2.5h-1Nitrogen is filled in the reaction process, the flow rate of the nitrogen is 800mL/min, and the reaction result is shown in Table 1.
Comparative example 1
Preparing a catalyst by adopting a coprecipitation method: 147.11g of Al (NO)3)3·9H2O、73.45g Zn(NO3)2·6H2O、183.49g Cu(NO3)2·3H2Placing O and 1g of sodium ethylene diamine tetracetate in a 5L glass stirring kettle with a circulating water bath, adding boiling water to a constant volume of 2L, starting stirring to completely dissolve the sodium ethylene diamine tetracetate, setting the stirring speed at 200r/min, and starting circulating heating at 80 ℃. And (3) when the temperature is stabilized at 80 +/-2 ℃, dropwise adding a 20% potassium carbonate aqueous solution into the glass stirring kettle, stopping dropwise adding when the pH of the mixed solution is 7-8, continuously stirring at constant temperature for 2h for precipitation reaction, and then putting into an oven at 80 ℃ for aging for 12 h. After aging, carrying out suction filtration, washing and drying, roasting at 450 ℃ for 4h, and grinding to particle size<500 meshes to obtain the catalyst precursor. And uniformly mixing 100g of catalyst precursor and 3g of graphite powder, and tabletting to obtain the catalyst. The subsequent catalytic dehydrogenation was carried out as in example 1. The reaction results are shown in Table 1.
TABLE 1 evaluation results of reaction of examples and comparative examples
Serial number Propylene glycol methyl ether conversion/%) Selectivity/% of methoxyacetone
Example 1 68.15 99.56
Example 2 65.59 99.38
Example 3 65.37 99.46
Example 4 62.94 99.41
Example 5 73.67 99.12
Example 6 61.36 99.53
Example 7 60.19 99.46
Example 8 65.15 99.89
Example 9 83.94 95.16
Example 10 68.42 98.26
Comparative example 1 54.98 80.26
As can be seen from Table 1, the performance of the copper-based catalyst prepared by secondary precipitation in the invention for preparing the methoxy acetone by catalytic dehydrogenation of propylene glycol methyl ether is superior to that of the copper-based catalyst prepared by one-time coprecipitation in comparative example 1.

Claims (8)

1. A method for preparing methoxy acetone by continuous catalytic dehydrogenation of propylene glycol methyl ether is characterized by comprising the following steps: propylene glycol methyl ether continuous catalytic dehydrogenation is carried out in a fixed bed to prepare methoxy acetone, a catalyst for catalytic dehydrogenation is prepared by fractional precipitation, a carrier is prepared by the first-level precipitation, active components are loaded by the second-level precipitation, the carrier is any one or two of zinc oxide, aluminum oxide and magnesium oxide, and the active components are any one or two of copper, nickel and cobalt or oxides thereof; the specific preparation method of the catalyst comprises the following steps:
(1) primary precipitation: under the conditions of heating and stirring, dropwise adding a precipitator into a soluble metal salt aqueous solution of the carrier, stopping dropwise adding the precipitator when the pH value of a mixed solution is 7-8, continuously stirring at a constant temperature for 30-120 min for carrying out a precipitation reaction, and then carrying out aging, suction filtration, washing, drying, roasting and grinding to obtain the carrier;
(2) secondary precipitation: uniformly mixing a carrier and a soluble metal salt aqueous solution of an active component, adding a metal complexing agent, dropwise adding a precipitator under the conditions of heating and stirring, stopping dropwise adding the precipitator when the pH value of the mixed solution is 7-8, continuously stirring at a constant temperature for 30-120 min for precipitation reaction, and then aging, filtering, washing, drying, roasting and grinding to obtain a catalyst precursor; wherein, the carrier accounts for 20-70% of the mass of the catalyst precursor, and the active component accounts for 30-80% of the mass of the catalyst precursor;
(3) uniformly mixing a catalyst precursor and graphite powder, and then tabletting and forming to obtain a catalyst; wherein, the adding amount of the graphite powder is 0.5 to 5 percent of the mass of the catalyst precursor.
2. The method for preparing methoxy acetone by continuously catalyzing and dehydrogenating propylene glycol methyl ether according to claim 1, which is characterized in that: the carrier is a mixture of zinc oxide or magnesium oxide and aluminum oxide, wherein the molar ratio of the zinc oxide or magnesium oxide to the aluminum oxide is 0.3-3: 1; the active component is any one of copper, cobalt or oxides thereof.
3. The process for the continuous catalytic dehydrogenation of propylene glycol methyl ether to methoxy acetone according to claims 1 and 2, characterized in that: the carrier accounts for 30-60% of the mass of the catalyst precursor, and the active component accounts for 40-70% of the mass of the catalyst precursor; the adding amount of the graphite powder is 2-5% of the mass of the catalyst precursor.
4. The method for preparing methoxy acetone by continuously catalyzing and dehydrogenating propylene glycol methyl ether according to claim 1, which is characterized in that: the soluble metal salt of the carrier and the soluble metal salt of the active component are nitrates; the precipitator is any one of sodium carbonate, sodium bicarbonate and potassium carbonate; the metal complexing agent is any one of sodium ethylene diamine tetracetate, sodium aminotriacetate and ethanolamine, and the addition amount of the complexing agent is 0.1-5% of the mass of the catalyst precursor.
5. The method for preparing methoxy acetone by continuously catalyzing and dehydrogenating propylene glycol methyl ether according to claim 1, which is characterized in that: the heating temperature is 50-95 ℃, and the stirring speed is 50-300 r/min; the aging temperature is 50-95 ℃ and the aging time is 1-24 h; the roasting temperature is 300-700 ℃, and the roasting time is 2-10 h.
6. The method for preparing methoxy acetone by continuous catalytic dehydrogenation of propylene glycol methyl ether according to claim 5, characterized in that: the heating temperature is 60-90 ℃, and the stirring speed is 100-200 r/min; the aging temperature is 60-90 ℃, and the aging time is 5-20 hours; the roasting temperature is 350-600 ℃, and the roasting time is 3-8 h.
7. The method for preparing methoxy acetone by continuously catalyzing and dehydrogenating propylene glycol methyl ether according to claim 1, which is characterized in that: the catalyst is reduced by hydrogen before reaction, the reduction temperature is 210-300 ℃, and the reduction time is 2-20 h.
8. The method for preparing methoxy acetone by continuously catalyzing and dehydrogenating propylene glycol methyl ether according to claim 1, which is characterized in that: the catalytic dehydrogenation reaction temperature is 200-300 ℃, the reaction pressure is 0-0.5 MPa, and the reaction space velocity is 0.3-3 h-1And filling nitrogen in the reaction process, wherein the flow rate of the nitrogen is 50-1000 mL/min.
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